Hardened artificial mass and process of preparing it



Patented May 12, 1931 UNITED STATES PATENT OFFICE -AB'1HUB V088, OIFBANKFORT-ON-THE-MAIN-HOOHST,

GERMANY, ASSIGNOB '1'0 1. G.

MANY, A. CORPORATION OF GERMANY EABDENED ARTIFICIAL IASE LND PROCESS OFPREPARING IT llo Drawing. Application fled September 18,

ing of or containing insoluble and infusible resins containingchemically entirely indifierent carboxyl groups.

have found that mfusible By this invention hardened artificialmaterials, havin valuable properties, are made by heating p enolaldehyderesins containing ro mol one or several carboxyl cups to a temperatureabove C. pre erably at about C. to C. in the presence or absence offillin materials. Furthermore and insoluble masses are obtained, if theabove-mentioned carboxyl-containing resins are heated in the presence ofpolyvalent alcohols, as for instance glycol glycerine, mannitol andpplyvinyl alcoho The aforesaid resins containing carboxylic acid groups(hereinafter referred to for convenience as resin-carboxylic acids) maybe obtained by reaction between a phenolaldehyde resin and a halogenfatty acid or a salt thereof, or by reaction between a phenoxyfatty acidand formaldehyde or a substance yieldin formaldehyde. I have moreoverfound t at insoluble and infusible resins are obtained by transformingthe said resins containing carboxyl grou s into water-soluble comapoundsby neutra izing them wholly or parti ly with ammonia or the derivativesthereof, as for instance methylamine or pyridine then evaporating theaqueous solution and beating the residue at a temperature between 100 C.and 200 0., preferably at about 150 C. to 160 C.

If desired, a filling material ma be associated with the agous solution0 the ammonium or other e of the resin-carboxylic acid. New artificialmaterials may, for instance, be made by impregnating paper-pulp with theueous solution, ressing into a suitable mol and hardening yheatmg. Byimlpre ating wood-paste, which is obtainab e c eaply in commerce, withthe solution, it is thus possible to manufacture molded articles'of anyshape, such as pipes, boxes, containers, dishes, casks, barrels, andother various kinds of articles of general utlhtyn.

1928, Serial No. 307,042, and in Germany September 28, 1927.

Artificial masses may also be made by impregnating paper web,superposing a number of layers of the impregnated web, and subsequentlyhardenin the mass.

The molded articles thus obtained have valuable properties; inparticular, they are entirely water-proof and extraordinarily resistantto mechanical and chemical action. According to the purpose for whichthe products are intended, there may be used instead of a paper-pul orweb another filling material, such as as stos fibers, sawdust,rnfusorial earth, powdered horn or the like. The products have a lowelectrical conductivity, and are, therefore, well suited for electricalinsulation. They are also applicable as substitutes for shellac and themanufacture of stifienin s for bats or caps.

By a urther feature of resin-carboxylic acids may be converted intouseful hardened products by heating their ammonium salts, or salts ofammonia derivaties at a temperature above 100 C. in the presenceof apolyhydric alcohol of low volatility, such as gycol, gl cerine,mannitol, polyvinyl aleoho a carbo ydrate soluble in water, or the like.The hardening operation may also in this case be conducted in presenceor absence of a fillin material. In this method of o crating, it is evenpossible to dis ense wit the conversion of the resincar oxylic acid intoits salt, and the invention accordin 1 includes a manufacture ofhardened arti cial material by heating a resin-carbox lie acid at atemperature at above 100 in the resence ofa polyhydric alcohol of lowvolati ity, with or .yvithout addition of a filling material, forexample, the resin-carboxylic acid is dissolved in alcohol, the solutionis mixed with a quantity of glycerine, equimolecular to that of theresin acid, or an equimolecular quantity of another polyhydric alcoholof low volatility, such as pentaerythritol, the solution is evaporatedand the residue hardened as already described. In some cases, thesolvent may be dispensed with, it bein sufiicient merely to mix theresin-carboxy '0 acid and the polyhydric alcohol, and toheat the mixtureto the necessary temperature.

the invention the Products of particularly good elasticity are obtainedby using as the polyvalent alcohol polyvinyl alcohol, obtainable bysaponification of olyvinyl acetate.

The ollowing examples illustrate the invention, the parts being byweight 120 parts of the artificial resin obtainable by reaction between140 parts of formaldehyde of 30 per cent strength and 110 parts ofcommercial cresol in the presence of an alkali, are dissolved in 250parts of concentrated caustic soda solution (42 B.) and 260 parts ofwater. Into the clear, somewhat viscous solution 90 parts of chloraceticacid are introduccd slowly in portions at a temperature between 50 C.and 60 C. The introduction of each portion causes spontaneous evolutionof heat and in order to avoid frothing the temperature is controlled sothat it does not exceed 80 C. When all the chloracetic acid has beenintroduced, the temperature is maintained for about 20 minutes at 100 C.to 102 C. The clear solution is diluted with several times its volume ofwater and the resin-carboxylic acid thus obtained is precipitated by theaddition of hydrochloric acid until the mass is acid in reaction. Theresin acid is freed by Washing from salt and other inorganic bodies. Thepaste so obtained is introduced whilst still moist into an aqueoussolution ofannnonia at a moderately raised temperature, preferably about60 (.-05 C. The strength and quantity of the solution are such that thequantity of ammonia used is equivalent to that of the resin acid, andamounts to about 17 parts of Nth: a smaller quantity ofammonia ishowevcr sufficient for obtaining a clear solution, which by reason ofthe presence of free carboxylic acid has an acid reaction. The acid orneutral solution may be used directly as such or it may be concentratedor diluted in any desired degree. It may be used for impregnatingpaper-pulp, or animal or vegetable tissues; it is also suitable forpreparing lacquers because the solution is easily applied to surfacesand yields on drying a. smooth lustrous film, which when heated to about150 C. becomes infusible and insoluble. In order to obtain the productin an anhydrous solid state it is suiiicient to evaporate the solutionadvantageously in a vacuum for the purpose of avoiding overheating. Theanhydrous product is a dry powder which likewise becomes insoluble andinfusible, with separation of ammonia and water vapour when heated to atemperature above 100 C. It is easily soluble in water and has, ascompared with the artificial resin known as Bakelite the advantage thatfor the preparation of solutions the use of relatively expensive organicsolvents may be avoided.

2) The resin-carboxylic acid (prepared as described in Example 1) isdissolved in an aqueous solution of yridine instead of in aqueousammonia. he hardened products obtainable from this solution in themanner already described are more elastic than those obtained asdescribed in Example 1, but less resistant to chemical action.

3) The resin-carboxylic acid obtainable by reaction between 30 parts ofparaformaldehydc and 100 parts of cresoxy-acetic acid in the presence ofhydrochloric acid is freed from electrolytes by Washing and thendissolved in 300 parts of an aqueous solution of methylamine of 8 percent strength. The solution may be used in the manner described inExample 1., for impregnating materials, for the preparation of lacquers,and for the manufacture of artificial objects of various kinds.

4) The resin-like product obtained by condensation of equal parts ofcommercial tricresol and formaldehyde of 30 per cent strength in thepresence of about 10 per cent of an alkali is mixed, without being freedfrom the alkali used for the condensation, with a quantity of aconcentrated aque ous solution of an alkali such that the total quantityof the alkali present is equivalent to the quantity of the cresol used.Into the clear aqueous solution thus obtained there is introduced in theform of a concentrated aqueous solution, a quantity of sodiumchloracetate also equivalent to the cresol used, at a temperature ofabout 60 C. C. To a condensation product obtained from 108 parts ofcresol, 108 parts of formaldehyde of 30 percent strength and 30 parts ofconcentrated caustic soda solution of 42 B., there are added to amoderate temperature (40* 50 (1.), a further 90 parts of caustic sodasolution and 116.5 parts of sodium chloracetate, the whole beingmaintained at about 40 C.- 50 C. until all sodium chloracetate has beenintroduced, after which it is heated for a short time at 95 C.100 C. forthe purpose of accelerating the reaction. The resin-acid product isprecipitated by acidification with hydrochloric acid; it is a whitishresinous mass which when cold easily crumbles, but becomes soft at amoderately raised temperature. It is washed, dissolved in 400 parts ofWarm aqueous ammonia of 10 per cent strength, and the clear, feeblycolored solution producedwhich has a slightly ammoniacal smell, is mixedwith an aqueous solution of 25 parts of polyvinyl alcohol. Afterevapcrating the solution so obtained on a water bath, there remains aclear resinous residue, I

5) 100 parts of the henol-formaldehyde condensation product nown asBakelite A, are caused to react in the manner already described withchloracetic acid, and the resin-acid thus obtained is dissolved inaqueous ammonia as described in Example 4. The aqueous solution is mixedwith 15 parts of glycerine of 97 per cent strength, the mixture iskneaded with a quantity of paper-pulp of 22 per cent strength, such thata uniform pasty mass is produced. The mass is freed from a art of thesolution by pressing, the solid ca e so obtained is pressed in suitablemolds which are then heated internally or externally. There are thusobtained homogeneous hardened objects which are very resistant tomechanical and chemical actions and are distin ished by their lowspecific gravity.

6) he condensation product prepared in the manner indicated in Example4. from tricresol, formaldehyde and chloroacetic acid is isolated fromits alkaline solution by acidiflying, washing out and drying. 100 artsof t e powdery resin-carboxylic acid t us obtained are mixed with threetimes its weight of diatomaceous earth, the mixture is filled into amold and maintained in the closed mold for y hours at a temperature ofabout 190 C. to 200 C. After cooling, the mass thus obtained may beremoved from the mold. It is very resistant and can be used for thepreparation of various commodities, as such for instance, as boxes,switchboards, telephone receivers or the like.

7) 125 parts of artificial resin, obtained by causing 40 parts ofparaldehyde to act upon 100 parts of technical cresol, and which issoluble in alkali are treated with 140 parts of bromo-propionic acid inthe manner described in the preceding examples. The isolated resin-caroxylic acid is melted and into the melt are introduced while wellstirring v for about 3 hours.

' small 35 parts of glycol at a temperature of about 130 C. The resinousmass is then heated in a mold to a temperature of from 180 C. to 190 C.and maintained at this temperature After cooling, :1 hard, elastic bodyis obtained, which is no longer fusible nor soluble in the known organicsolvents.

8) By causing 40 parts of araformaldehyd e' to act for about half an ourat 13. to C. upon 100 parts of phenol with a uantity of a catalyst addedthereto, as for instance parts of lactic acid, there is obtained a resinwhich is treated in its alkaline solution with chloroacetic acid in themanner indicated in the foregoing examples. The isolatedresin-carboxylic acid is dissolved in alcohol of three times its weight,to the solution are added 30 parts of sorbitol and the alcohol is thendistilled off in vacuo. The remaining resinous mass is then mixed with250 arts of casein, the mixture is filled 66 into mol s and hardened byheating it for several hours to 150 C. to 160 C. The artificial massthus obtained is very suitable for isolating purposes and for use inelectrotechnics.

I claim 1. The process which consists in heating phenolaldehydecondensation products containing carboxyl groups to a temperature ofbetween 100 C. and 200 C.

2. The process which consists in heating condensation products, obtainedfrom a phenolaldehyde resin and a halogen fatty acid, 'to a temperatureof between 100 C. and 200 C.

3. The process which consists in heating condensation products, obtainedfrom chloroacetic acid and the condensation product of phenol andformaldehyde, to a temperature of between 100 C. and 200 C.

4. The process which consists in heating phenolaldehyde condensationroducts containing carboxyl groups with t e addition of a polyvalentalcohol to a temperature of between 100 C. and 200 C.

5. The process which consists in heating condensation products, obtainedfrom a phenolaldehyde resin and a hologen fatty acid with the additionof a polyvalent alcohol to a temperature of between 100 C. and 200 C.

6. The process which consists in heating condensation products, obtainedfrom chloroacetic acid and the condensation product of phenol andformaldehyde with the addition of a polyvalent alcohol to a temperatureof between 100 C. and 200 C.

7. The process which consists in heating condensation products, obtainedfrom chloroacetic acid and the condensation product of phenol andformaldehyde, with the addition of glcerine to a temperature of between100 and 200 C.

8. As new products, insoluble and infusible resins containing chemicallyentirely indifferent carboxyl groups, substantially identical withresins obtainable by heating phenolaldehyde condensation productscontaining carboxyl groups to a temperature of between 100 C. and 200 C.

9. As new products, insoluble and infusible resins containing chemicallyentirely indifferent carboxyl groups, substantial y identical withresins obtainable by heatin condensation products, obtained from a penolaldehyde resin and a halogen fatty acid to a temperature of between100 C. and 200 C.

10. As new products, insoluble and infusible resins containingchemically entirely indifferent carboxyl groups, substantially identicalwith resins obtainable by heating condensation products, obtained fromchloroacetic acid and the condensation product of henol andformaldehyde, to a temperature of etween 100 C. and 200 C.

11. As new products, insoluble and infuion sible resins containingchemically entirely indifferent carboxyl grou s, substantially identicalwith resins obtaina 1e by heating phenolaldehyde condensation productscontaining carboxyl groups with the addition of a polyvalent alcohol toa temperature of between C. and 200 C.

12. As new products, insoluble and infusible resins containingchemically entirely indifierent carboxyl roups, substantially identicalwith resins o tainable by heating condensation products, obtained from aphenolaldehyde resin and a halogen fatty acid, with the addition of apolyvalent alcohol to a temperature of between 100 C. and 200 C.

13. As new products insoluble and infusible resins containing chemicallyentirely indifferent carboxyl roups, substantially identical with resins'o tainable by heating condensation products, obtained from chloroaceticacid and the condensation productof phenol and formaldehyde, with theaddition of a polyvalent alcohol to a temperature of between 100 C. and200 C.

14. As new products, insoluble and infusible resins containingchemically entirely indifferent carboxyl groups, substantially identicalwith resins obtainable by heating condensation products, obtained fromchloroacetic acid and the condensation product of phenol andformaldehyde, with the addition of g1 cerine to a temperature of between100 and 200 C.

In testimony whereof, I afiix my signature.

DR. ARTHUR VOSS.

sible resins containing chemically entirely in different carboxyl grous, substantially identical with resins obtaina le by heatingphenolaldehyde condensation products containing 5 carboxyl grou s withthe addition of a polyvalent alcoho to a temperature of between 100 C.and 200 C.

12. As new products, insoluble and infusible resins containingchemically entirely m indifferent oarboxyl roups, substantiallyidentical with resins o tainable by heating condensation products,obtained from a phenolaldehyde resin and a halogen fatty acid, with theaddition of a polyvalent alcohol to a temperature of between 100 C. and200 C.

13. As new products insoluble and infusible resins containing chemicallyentirely indifferent carboxyl oups, substantially identical with resinso tainable by heatin con- 0 densation products, obtained from cliloroacetic acid and the condensation product of phenol andformaldehyde, with the addition of a polyvalent alcohol to a temperatureof between 100 C. and 200 C. y 14. As new products, insoluble andinfusible resins containing chemically entirely indifferent carboxylgroups, substantially identical with resins obtainable by heatingcondensation products, obtained from chloroacetic acid and thecondensation product of phenol and formaldehyde, with the addition ofglgcerine to a temperature of between 100 and 200 C. y

In testimony whereof, I aflix my signature. DR. ARTHUR VOSS.

CERTIFICATE OF CORRECTION.

Patent No. 1,805,385; Granted May 12, 1931, to

ARTHUR voss.

It is hereby certified that error appears in the printed apeciticationof the above numbered patent requiring correction as follows: Page 3,line 28, for the fraction "1" read 1-2, and line 55, for "2/3" read 2-3;and that the said Lettera Patent should be read with these correctionstherein that the same may conform to the record of the case in thePatent Office.

Signed and aealed this 14th day of July, A. D. 1931.

ll. 1. Moore, (Seal) Acting Commissioner of Patents.

CERTIFICATE OF CORRECTION.

Pmm No. 1.805385 Granted May 11 1931. m

ARTHUR voss.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows; Page 3,line 28, for the traction "i" read 1-2, and line 55, for "2/3" read 2-3;and that the said Letters Patent should be read with these correctionstherein that the name may conform to the recon! of the case in thePatent Office.

Signed and sealed this 14th day of July, A. D. 1931.

II. J. Moore, (Seal) Acting Commissioner of Patents.

